
硅橡膠是(shi)指主鏈由硅(gui)和氧(yang)原(yuan)子交(jiao)替構成,硅(gui)原(yuan)子上(shang)通常(chang)連有(you)兩個有(you)機基(ji)團的(de)(de)(de)(de)(de)橡(xiang)(xiang)(xiang)膠(jiao)。普通的(de)(de)(de)(de)(de)硅(gui)橡(xiang)(xiang)(xiang)膠(jiao)主要(yao)由含甲基(ji)和少量乙(yi)烯基(ji)的(de)(de)(de)(de)(de)硅(gui)氧(yang)鏈節組(zu)成。苯基(ji)的(de)(de)(de)(de)(de)引(yin)(yin)(yin)入可(ke)(ke)提高(gao)硅(gui)橡(xiang)(xiang)(xiang)膠(jiao)的(de)(de)(de)(de)(de)耐高(gao)、低溫性(xing)(xing)能(neng)(neng),三氟丙基(ji)及氰基(ji)的(de)(de)(de)(de)(de)引(yin)(yin)(yin)入則可(ke)(ke)提高(gao)硅(gui)橡(xiang)(xiang)(xiang)膠(jiao)的(de)(de)(de)(de)(de)耐溫及耐油性(xing)(xing)能(neng)(neng)。硅(gui)橡(xiang)(xiang)(xiang)膠(jiao)耐低溫性(xing)(xing)能(neng)(neng)良(liang)好,一般(ban)在(zai)-55℃下仍能(neng)(neng)工作(zuo)。引(yin)(yin)(yin)入苯基(ji)后,可(ke)(ke)達-73℃。硅(gui)橡(xiang)(xiang)(xiang)膠(jiao)的(de)(de)(de)(de)(de)耐熱性(xing)(xing)能(neng)(neng)也(ye)(ye)很突出(chu),在(zai)180℃下可(ke)(ke)長期工作(zuo),稍高(gao)于(yu)200℃也(ye)(ye)能(neng)(neng)承(cheng)受數(shu)周(zhou)或更長時間仍有(you)彈(dan)性(xing)(xing),瞬時可(ke)(ke)耐300℃以(yi)上(shang)的(de)(de)(de)(de)(de)高(gao)溫。硅(gui)橡(xiang)(xiang)(xiang)膠(jiao)的(de)(de)(de)(de)(de)透(tou)氣性(xing)(xing)好,氧(yang)氣透(tou)過率在(zai)合成聚(ju)合物中是(shi)較(jiao)高(gao)的(de)(de)(de)(de)(de)。此(ci)外,硅(gui)橡(xiang)(xiang)(xiang)膠(jiao)還(huan)具(ju)有(you)生理惰性(xing)(xing)、不會(hui)導致凝血的(de)(de)(de)(de)(de)突出(chu)特(te)性(xing)(xing),因此(ci)在(zai)醫用領域應用廣泛。
主要品種
硅(gui)(gui)橡(xiang)膠(jiao)(jiao)分類的(de)(de)方法(fa)很多,通常按(an)固化(hua)前(qian)的(de)(de)形態分為固體(ti)(ti)硅(gui)(gui)橡(xiang)膠(jiao)(jiao)和液體(ti)(ti)硅(gui)(gui)橡(xiang)膠(jiao)(jiao);按(an)硫(liu)(liu)化(hua)溫(wen)度分為室溫(wen)硫(liu)(liu)化(hua)硅(gui)(gui)橡(xiang)膠(jiao)(jiao),高(gao)溫(wen)硫(liu)(liu)化(hua)硅(gui)(gui)橡(xiang)膠(jiao)(jiao);按(an)所用(yong)單體(ti)(ti)的(de)(de)不(bu)同(tong),可分為甲基乙烯基硅(gui)(gui)橡(xiang)膠(jiao)(jiao),甲基苯基乙烯基硅(gui)(gui)橡(xiang)膠(jiao)(jiao)、氟硅(gui)(gui),腈(jing)硅(gui)(gui)橡(xiang)膠(jiao)(jiao)等;按(an)性(xing)能和用(yong)途的(de)(de)不(bu)同(tong)又可分為通用(yong)型、超(chao)耐(nai)低溫(wen)型、超(chao)耐(nai)高(gao)溫(wen)型、高(gao)強力型、耐(nai)油型、醫用(yong)型等等。
發展史
硅(gui)(gui)(gui)橡(xiang)膠(jiao)早期是由(you)美(mei)國(guo)(guo)以三氯(lv)化鐵(tie)為催化劑合成的(de)(de)。1945年(nian),硅(gui)(gui)(gui)橡(xiang)膠(jiao)產品問世。1948年(nian),采用(yong)高比表(biao)面積的(de)(de)氣(qi)相法白炭黑(hei)補強的(de)(de)硅(gui)(gui)(gui)橡(xiang)膠(jiao)研(yan)制(zhi)成功,使硅(gui)(gui)(gui)橡(xiang)膠(jiao)的(de)(de)性能躍升到(dao)實用(yong)階段,奠定了現代硅(gui)(gui)(gui)橡(xiang)膠(jiao)生產技術的(de)(de)基礎。從二甲基二氯(lv)硅(gui)(gui)(gui)烷(wan)合成開始生產硅(gui)(gui)(gui)橡(xiang)膠(jiao)的(de)(de)國(guo)(guo)家(jia)(jia)有美(mei)國(guo)(guo)。俄羅斯(si)、德(de)國(guo)(guo)、日本(ben)、韓(han)國(guo)(guo)和中(zhong)(zhong)國(guo)(guo)等(deng)。中(zhong)(zhong)國(guo)(guo)硅(gui)(gui)(gui)橡(xiang)膠(jiao)的(de)(de)工業化研(yan)究始于1957年(nian),多家(jia)(jia)研(yan)究所和企業陸續開發出各種硅(gui)(gui)(gui)橡(xiang)膠(jiao)。到(dao)2003年(nian)底(di),中(zhong)(zhong)國(guo)(guo)硅(gui)(gui)(gui)橡(xiang)膠(jiao)生產能力(li)為135千(qian)噸,其中(zhong)(zhong)高溫膠(jiao)100千(qian)噸。
高溫硫化硅橡膠
高溫硫化(hua)(hua)(hua)(hua)硅(gui)橡膠(jiao)是指聚(ju)硅(gui)氧(yang)烷變(bian)成(cheng)(cheng)彈性(xing)(xing)體的過程是經過高溫(110-170℃)硫化(hua)(hua)(hua)(hua)成(cheng)(cheng)型的。它主(zhu)要以(yi)高分(fen)子量(liang)的聚(ju)甲基乙烯基硅(gui)氧(yang)烷為生膠(jiao),混入補強填料、硫化(hua)(hua)(hua)(hua)劑等(deng),在加熱加壓下(xia)硫化(hua)(hua)(hua)(hua)成(cheng)(cheng)彈性(xing)(xing)體。硅(gui)橡膠(jiao)的補強主(zhu)要是各(ge)種(zhong)(zhong)類型的白炭黑,可使(shi)硫化(hua)(hua)(hua)(hua)膠(jiao)的強度增加數十倍。有(you)時(shi)為了降低成(cheng)(cheng)本或(huo)改善(shan)膠(jiao)料性(xing)(xing)能(neng)及賦予硫化(hua)(hua)(hua)(hua)膠(jiao)各(ge)種(zhong)(zhong)特殊的性(xing)(xing)能(neng),也加入相應(ying)的各(ge)種(zhong)(zhong)添加劑。硫化(hua)(hua)(hua)(hua)劑是各(ge)種(zhong)(zhong)有(you)機過氧(yang)化(hua)(hua)(hua)(hua)物或(huo)加成(cheng)(cheng)反(fan)應(ying)催化(hua)(hua)(hua)(hua)劑。
加工(gong)成(cheng)型方法如圖(tu)所示。一(yi)次(ci)硫化(hua)(hua)的(de)(de)(de)目的(de)(de)(de)是進行高分子鏈(lian)的(de)(de)(de)交聯(lian)反應(ying);二次(ci)硫化(hua)(hua)的(de)(de)(de)目的(de)(de)(de)是進行補充(chong)交聯(lian)、驅除硫化(hua)(hua)劑(ji)分解產物(wu)和其他揮發性化(hua)(hua)合物(wu)以穩定硫化(hua)(hua)膠的(de)(de)(de)各項性能(neng)。常(chang)用(yong)的(de)(de)(de)設備有開放(fang)式煉膠機(ji)、捏合機(ji)及真空密煉機(ji)。
主要性能
(1)高溫(wen)(wen)(wen)(wen)性(xing)(xing)(xing)(xing)(xing)能(neng)(neng)(neng)(neng)(neng)。硅(gui)橡(xiang)(xiang)(xiang)(xiang)膠(jiao)(jiao)(jiao)顯(xian)著的(de)(de)(de)特征(zheng)是(shi)高溫(wen)(wen)(wen)(wen)穩定(ding)(ding)性(xing)(xing)(xing)(xing)(xing),雖(sui)然(ran)常(chang)溫(wen)(wen)(wen)(wen)下(xia)(xia)(xia)硅(gui)橡(xiang)(xiang)(xiang)(xiang)膠(jiao)(jiao)(jiao)的(de)(de)(de)強度僅(jin)是(shi)天然(ran)橡(xiang)(xiang)(xiang)(xiang)膠(jiao)(jiao)(jiao)或某些(xie)合成(cheng)橡(xiang)(xiang)(xiang)(xiang)膠(jiao)(jiao)(jiao)的(de)(de)(de)一半,但(dan)在(zai)200℃以上的(de)(de)(de)高溫(wen)(wen)(wen)(wen)環境下(xia)(xia)(xia),硅(gui)橡(xiang)(xiang)(xiang)(xiang)膠(jiao)(jiao)(jiao)仍能(neng)(neng)(neng)(neng)(neng)保持一定(ding)(ding)的(de)(de)(de)柔韌(ren)性(xing)(xing)(xing)(xing)(xing)、回彈性(xing)(xing)(xing)(xing)(xing)和(he)表面硬度,且力(li)學性(xing)(xing)(xing)(xing)(xing)能(neng)(neng)(neng)(neng)(neng)無(wu)明顯(xian)變化(hua)(hua)。(2)低(di)溫(wen)(wen)(wen)(wen)性(xing)(xing)(xing)(xing)(xing)能(neng)(neng)(neng)(neng)(neng)硅(gui)橡(xiang)(xiang)(xiang)(xiang)膠(jiao)(jiao)(jiao)的(de)(de)(de)玻璃化(hua)(hua)溫(wen)(wen)(wen)(wen)度一般為(wei)-70~-50℃,特殊配方可達-100℃,表明其低(di)溫(wen)(wen)(wen)(wen)性(xing)(xing)(xing)(xing)(xing)能(neng)(neng)(neng)(neng)(neng)優(you)(you)異。這對航(hang)空、宇航(hang)工業的(de)(de)(de)意義重大。(3)耐(nai)(nai)候性(xing)(xing)(xing)(xing)(xing)硅(gui)橡(xiang)(xiang)(xiang)(xiang)膠(jiao)(jiao)(jiao)中(zhong)Si-O-Si鍵對氧、臭(chou)氧及(ji)紫外線(xian)等(deng)(deng)十分穩定(ding)(ding),在(zai)不(bu)加任何添加劑的(de)(de)(de)情(qing)況下(xia)(xia)(xia),就(jiu)具有(you)(you)優(you)(you)良的(de)(de)(de)耐(nai)(nai)候性(xing)(xing)(xing)(xing)(xing)。(4)電(dian)氣性(xing)(xing)(xing)(xing)(xing)能(neng)(neng)(neng)(neng)(neng)。硅(gui)橡(xiang)(xiang)(xiang)(xiang)膠(jiao)(jiao)(jiao)具有(you)(you)優(you)(you)異的(de)(de)(de)絕(jue)緣性(xing)(xing)(xing)(xing)(xing)能(neng)(neng)(neng)(neng)(neng),耐(nai)(nai)電(dian)暈性(xing)(xing)(xing)(xing)(xing)和(he)耐(nai)(nai)電(dian)弧性(xing)(xing)(xing)(xing)(xing)也非常(chang)好。(5)物理機械性(xing)(xing)(xing)(xing)(xing)能(neng)(neng)(neng)(neng)(neng)。硅(gui)橡(xiang)(xiang)(xiang)(xiang)膠(jiao)(jiao)(jiao)常(chang)溫(wen)(wen)(wen)(wen)下(xia)(xia)(xia)的(de)(de)(de)物理機械性(xing)(xing)(xing)(xing)(xing)能(neng)(neng)(neng)(neng)(neng)比通用橡(xiang)(xiang)(xiang)(xiang)膠(jiao)(jiao)(jiao)差,但(dan)在(zai)150℃的(de)(de)(de)高溫(wen)(wen)(wen)(wen)和(he)-50℃的(de)(de)(de)低(di)溫(wen)(wen)(wen)(wen)下(xia)(xia)(xia),其物理機械性(xing)(xing)(xing)(xing)(xing)能(neng)(neng)(neng)(neng)(neng)優(you)(you)于通用橡(xiang)(xiang)(xiang)(xiang)膠(jiao)(jiao)(jiao)。(6)耐(nai)(nai)油及(ji)化(hua)(hua)學試劑性(xing)(xing)(xing)(xing)(xing)。普通硅(gui)橡(xiang)(xiang)(xiang)(xiang)膠(jiao)(jiao)(jiao)具有(you)(you)中(zhong)等(deng)(deng)的(de)(de)(de)耐(nai)(nai)油、耐(nai)(nai)溶劑性(xing)(xing)(xing)(xing)(xing)能(neng)(neng)(neng)(neng)(neng)。(7)氣體透(tou)(tou)過性(xing)(xing)(xing)(xing)(xing)能(neng)(neng)(neng)(neng)(neng)。室(shi)溫(wen)(wen)(wen)(wen)下(xia)(xia)(xia)硅(gui)橡(xiang)(xiang)(xiang)(xiang)膠(jiao)(jiao)(jiao)對空氣、氮、氧、二氧化(hua)(hua)碳等(deng)(deng)氣體的(de)(de)(de)透(tou)(tou)氣性(xing)(xing)(xing)(xing)(xing)比天然(ran)橡(xiang)(xiang)(xiang)(xiang)膠(jiao)(jiao)(jiao)高出30-50倍(bei)。(8)生理惰性(xing)(xing)(xing)(xing)(xing)。硅(gui)橡(xiang)(xiang)(xiang)(xiang)膠(jiao)(jiao)(jiao)無(wu)毒,無(wu)味(wei),無(wu)嗅,與(yu)人(ren)體組織不(bu)粘連,具有(you)(you)抗(kang)凝血(xue)作用,對肌體組織的(de)(de)(de)反應性(xing)(xing)(xing)(xing)(xing)非常(chang)少。特別適(shi)合作為(wei)醫用材料。
硅橡膠的用量
據中(zhong)國(guo)汽(qi)(qi)(qi)(qi)車(che)(che)工業協會統計,2012年(nian),汽(qi)(qi)(qi)(qi)車(che)(che)產銷(xiao)分別達到(dao)1927.18萬(wan)輛(liang)和1930.64萬(wan)輛(liang),同比分別增長(chang)4.63%和4.33%,汽(qi)(qi)(qi)(qi)車(che)(che)工業硅(gui)(gui)橡膠的(de)用量(liang)(liang)約達2.0萬(wan)t。根(gen)據觀研天(tian)下的(de)新研究(jiu),增加有機硅(gui)(gui)材料在汽(qi)(qi)(qi)(qi)車(che)(che)零部(bu)件(jian)(jian)方面的(de)用量(liang)(liang),可以大幅度提高汽(qi)(qi)(qi)(qi)車(che)(che)的(de)安全性(xing)能,因此,汽(qi)(qi)(qi)(qi)車(che)(che)產量(liang)(liang)和單車(che)(che)用量(liang)(liang)水(shui)平的(de)提高都將推(tui)動汽(qi)(qi)(qi)(qi)車(che)(che)工業對硅(gui)(gui)橡膠需求的(de)增加。國(guo)家(jia)鼓勵(li)自(zi)主(zhu)(zhu)品(pin)牌(pai)(pai)的(de)汽(qi)(qi)(qi)(qi)車(che)(che)發(fa)展,關鍵汽(qi)(qi)(qi)(qi)車(che)(che)零部(bu)件(jian)(jian)實現自(zi)主(zhu)(zhu)化,《2012年(nian)度黨(dang)政機關公務用車(che)(che)選用車(che)(che)型目錄(征求意見稿)》為自(zi)主(zhu)(zhu)品(pin)牌(pai)(pai)擴大在政府采購(gou)的(de)市場份額,為改變目前(qian)國(guo)內政府采購(gou)以合資(zi)品(pin)牌(pai)(pai)產品(pin)為主(zhu)(zhu)的(de)局面提供了保(bao)(bao)障。促進自(zi)主(zhu)(zhu)品(pin)牌(pai)(pai)發(fa)展,國(guo)產汽(qi)(qi)(qi)(qi)車(che)(che)業的(de)繁榮將為汽(qi)(qi)(qi)(qi)車(che)(che)膠的(de)應(ying)用提供有力保(bao)(bao)障。預測未(wei)來3年(nian),我(wo)國(guo)室溫硫化硅(gui)(gui)橡膠在汽(qi)(qi)(qi)(qi)車(che)(che)行業將以年(nian)均20%增長(chang)。
此外,硅(gui)橡(xiang)膠(jiao)(jiao)是重要的(de)(de)(de)(de)(de)非(fei)石(shi)油(you)基合(he)成(cheng)(cheng)(cheng)橡(xiang)膠(jiao)(jiao),約占非(fei)石(shi)油(you)基合(he)成(cheng)(cheng)(cheng)橡(xiang)膠(jiao)(jiao)消費(fei)量的(de)(de)(de)(de)(de)98%。但(dan)因為石(shi)油(you)價格的(de)(de)(de)(de)(de)大(da)(da)幅(fu)上漲,同(tong)時(shi)我(wo)(wo)國(guo)在硅(gui)橡(xiang)膠(jiao)(jiao)的(de)(de)(de)(de)(de)關(guan)鍵(jian)原(yuan)料(liao)有(you)機(ji)(ji)硅(gui)單體(ti)(ti)的(de)(de)(de)(de)(de)生產技術方面(mian)取(qu)得突破,有(you)機(ji)(ji)硅(gui)單體(ti)(ti)的(de)(de)(de)(de)(de)生產技術在2005年(nian)(nian)前被幾家跨國(guo)公司壟斷,但(dan)目前我(wo)(wo)國(guo)已發展(zhan)成(cheng)(cheng)(cheng)為全球有(you)機(ji)(ji)硅(gui)單體(ti)(ti)第1大(da)(da)國(guo),這2個方面(mian)原(yuan)因使硅(gui)橡(xiang)膠(jiao)(jiao)的(de)(de)(de)(de)(de)價格從2011年(nian)(nian)起開始低于石(shi)油(you)基合(he)成(cheng)(cheng)(cheng)橡(xiang)膠(jiao)(jiao),僅約為大(da)(da)宗石(shi)油(you)基橡(xiang)膠(jiao)(jiao)的(de)(de)(de)(de)(de)80%~90%,成(cheng)(cheng)(cheng)為廉(lian)價的(de)(de)(de)(de)(de)合(he)成(cheng)(cheng)(cheng)橡(xiang)膠(jiao)(jiao),并開始大(da)(da)規模替代石(shi)油(you)基合(he)成(cheng)(cheng)(cheng)橡(xiang)膠(jiao)(jiao)。這將極大(da)(da)拓展(zhan)有(you)機(ji)(ji)硅(gui)產業的(de)(de)(de)(de)(de)市場空間,同(tong)時(shi)將帶動(dong)硅(gui)油(you)、硅(gui)烷(wan)偶聯劑和(he)硅(gui)樹脂等其他有(you)機(ji)(ji)硅(gui)產品的(de)(de)(de)(de)(de)消費(fei)。